Vanadium oxide semiconductors and method of manufacturing same

ABSTRACT

A THERMISTOR HAVING AN ABRUPT CHANGE IN A NEGATIVE TEMPERATURE COEFFICIENT OF ELECTRICAL RESISTANCE IN A SPECIFIC TEMPERATURE RANGE FROM 65 TO 70*C., WHICH COMPRISES A SINTERED BODY COMPOSED OF A SEMICONDUCTIVE OXIDE SUBSTANCE AND A PLURALITY OF CRYSTALLINE PARTICLES OF V204 SUSPENDED IN AND ENCLOSED BY SAID OXIDE SUBSTANCE. THIS SPECIFICATION ALSO DISCLOSES METHODS FOR PRODUCING THEREOF WHICH COMPRISES THE STEPS OF REDUCING A MIXTURE OF V2O5 AND OTHER OXIDE AT ABOUT 400*C. AND SINTERING THE REDUCED MIXTURE AT 1000-1300*C.

Aug. 10, 1971 HISAO FUTAKI ETAL 3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME FiledSept. 21, 1967 46 Sheets-Sheet 1 FIG.|

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TEMPERATURE (C) INVENTORS HIsno Furm BY TRKESHI' sm'Monn zlulnrtl WmlemAug. 10, 1971 HlsAQ FUTAK| ETAL 3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME FiledSept. 21, 1967 46 Sheets-Sheet I '1. FIG. 2

a 204 m 2 s 0 x m E m 20 -2OO |OO 0 I00 200 300 400 T EMPERATU RE (C)INVENTORS msno FuLTHKI' BY THKESM sumonn Aug. 10, 1971 HISAO FUTAKI ETAL3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME FiledSept. 21, 1967 46 Sheets-Sheet 5 FIG. 4

MIXING OF COMPOSITIONS STEP I GRINDING-MIXING STEP 2 MELTlNG-MIXING STEP3 CRUSHING STEP 4 REDUCTION TREATMENT STEP 5 MOLDING STEP 6SINTERTREATMENT STEP 7 THERMISTER STEP 8 INVENTORS Hnsno Fu'rm BYTHKESl-H SHIMUIDH 10, 1971 HISAO FUTAKI E L VANADIUM OXIDESEMICONDUCTORS AND METHOD OF MANUFACTURING SAME 46 Sheets-Sheet 4 FiledSept. 21, 1967 a l 6 .2 W O 4 5 O h 52 O 5 0 w 9w 5 m m 5 O 8 A w x O 65 4 3 2 l O 24 m w m m m m m o 0 FIG. 5

TEMPERATURE (C) )INVENTORS msflo FuTfiKi BY THKESHI smmnn alum, mJIPHI1971 HISAO FUTAKI ETA VANADIUM OXIDE SEMICONDUCTORS AND METHOD OFMANUFACTURING SAME 46 Sheets-Sheet 5 Filed Sept. 21, 1967 FIG. 6

r 4 3 o m m AS wozfimmwm IO 0 m TEST TIME (DAY) 5 m R mwm i N w N M II EmK Hun T Y B Aug. 10, 1971 H|$A0 F T ETAL 3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME FiledSept. 21, 1967 46 Sheets-Sheet 6 F IGQ 7 L=i= w 7O6 2 m4 l Q -703 m 704g/ W a I O IO 20 30 TEST TIME (DAY) INVENTORS msnofuT am BY TflksmSmMODfi Aug. 10, 1971 HISAO FUTAKI ETAL 3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME 46Sheets-Sheet 7 Filed Sept. 21. 1967 FIG. 8

TEMPERATURE (C) v INVENTORS HI SRO FMTRKI BY TRKESMI SMMODH Aug. '10,1971 H|sAQ FUTAKI ETAL 3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME FiledSept. 21. 1967 46 Sheets-Sheet 8 FIG. IO

N m m o ww m E. an Q m rlllil|lll llll OE 8R U T A m P M F- T 7 6 5 4 32 l 0% w m w m w w w 0 AS wuzfiflmwm Q m\ 9 E WW 6 mm F P M E T Aug. 10,1971 s o FUTAK] ETAL 3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING sAME FiledSept. 21, 1967 46 Sheets-Sheet 10 E's 4.0- Z a o 8 3.0 z u. 3 20- E 8 n:m 1.0-. I

O 60 I20 2&0 4o

REDUCE-TREATING TIME Tx (min) 6 ts 5 0 E, Z a 0 2- m 3 u. CE 0 LLI 1 (IO 480 REDUCE-TREATNIG TIME Tx (min.)

INVENTOR HISBO FHTHK' BY TnKEsm' suiMonn Aug. 10, 1971 5 0 FUTAK| ErAL3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME FiledSept. 21, 1967 46 Sheets-Sheet 11 FIG. I6

REDUCE-TREATING TIME 4 3 2 I CZ mozfiwawm o uwzis Enmm to 5% Tx (min.)

FIG. I7

REDUCE-TREATING TIME 4 3 2 Qs mozfimamm 6 32 26 K352 o NEE TX (min).INVENTORS HISHO PufrflKl Y THKESHi smMobn Aug. 10, 1971 HISAO FUTAKIETAL 3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME 46Sheets-Sheet 13 Filed Sept. 21, 1967 FIG.2O

COMPOSITIONAL RATIO R(moL%) COMPOSITIONAL RATIO R(mol%) O5 325.925 6 mwzzo Enmm 6 NEE FIG.2I

3 2 Q: mozfimamm 6 Nazis E3? to P21 3 2 Q2 mozfimawm no 3236 Enmm 6 NEECOMPOSITIONAL RATIO R(mOL%) COMPOSITIONAL RATIO R(moL !NVENTOR 5 HISHOmTnKI BY TFIKEsIII' SHIMODH Aug. 10, 1971 s o FUTAK| ETAL 3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME 46Sheets-Sheet 14 Filed Sept. 21. 1967 FIG.24

IO 0 so COMPOSITIONAL RATIO R(m0L lo'oso so COMPOSITIONAL RATIO R(m0l.%)

CE @2593. 6 wwzdio E52 6 NEE 0 IO 20 3o 40 COMPOSITIONAL RATIO R(moLCOMPOSITIONAL RATIO R(m0L 0 IO 20 3O 3 2 l CZ muzfimamm to $25 6 K313 oWEE INVENTORS msno fmflm BY TFIKESI'H SHIMODH Aug. 10, 1971 HISAO FUTAKIETAL 3,5Qfi fi OXIDE SEMICONDUCTORS AND METHOD VANADIUM OF MANUFACTURINGSAME 46 Sheets-Sheet 15 Filed Sept. 21, 1967 IO 20 3O 4O 5OCOMPOSITIONAL RATIO R0110.

. CZ wozfimamm .0 $236 Eamm 6 wbE 0 IO 5O 4O 5O COMPOSITIONAL RATIOR(m0L 5 AA v: 3 h

gs 32523. 6 wwzfi Ham? 6 NEE FIG.3O

FIG.29

IO 20 3O 4O 5O COMPOSITIONAL RATIO RUTIOI.

a z I $5 3252mm .6 323 6 .E:mm o NEE 0 IO 20 so COMPOSITIONAL RATIOR(m0L 2 is wozfibamm 6 mwz zo ESE? to E5.

mvENTom Hisao Fumm BY THKESM SFIIHQDH Aug. 10, 1971 HISAO FUTAKI EI'ALVANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME FiledSept. 21, 1967 RESISTANCE ((1) 46 Sheets-Sheet 16 TEMPERATURE (C) BY'rnmssui snimonn Aug. 10, 1971 HISAO FUTAKI ETAL 3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME FiledSept. 21, 1967 46 Sheets-Sheet 17 F I G. 32 F l G. 33

RESISTANCE/(H) (N I 8 a; N O

CD RESISTANCE ([1) TEMPERATURE (C) TEMPERATURE (C) INVENTORS m'sno imamBY 'Trmesm smnonn A (fa wan] mailer RESISTANCE (n) Aug. 10, 1971 HISAOFUTAKI ETAL 3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME FiledSept. 21, 1967 4 6 Sheets-Sheet 18 F G 34 F (5.35 I08 07 RESISTANCE (Q)I0 IO" 1 40 6O 8O I00 40 6O 80 I00 TEMPERATURE (C) TEMPERATURE (C)INVENTORS HI SHO FHTHKI BY TR KESI'H SHINODFI fi (Lila (1 rrl 7749.51405];

Aug. 10, 1971 HISAO FUTAKI ETAL 3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME FiledSept. 21, 1967 46 Sheets-Sheet 19 F l G. 37

m F l G. 36

I vfil 3708 RESISTANCE (n) RESISTANCE (n) W V w? 0 27:1?2

5604 -3704 loo seoq I 40 6O 80 I00 40 6O 80 I00 TEMPERATURE (C)TEMPERATURE C) INVENTORS Hisnd" Fumm' BY Tnxeini suinonn Jr/wan! madamAug. 10, 1971 5 0 FUTAK] ETAL 3,598,762

VANADIUM OXIDE SEMICONDUCTORS AND METHOD OF MANUFACTURING SAME FiledSept. 21, 1967 46 Sheets-Sheet 20 F l G. 38

TEST TIME (DAY) INVENTORS Hisnq Fujnm BY TflKEsm .SmMODB

